DE10053890A1 - Polyurethanes and polymer mixtures containing sulfide groups on this basis, as well as their preparation and their use - Google Patents

Abstract

Polyurethanes containing sulphide groups, including at least one group of general formula I in the main polymer chain and/or at least one group of general formula II at the chain terminus: -X-A-S-B-Y- (I)-X-A-S-B-YH (II), where the variables have the following meanings: S = sulphur atom; X and Y independently = oxygen atoms, sulphur atoms or groups -NZ with Z = hydrogen atom or alkyl residue with 1 to 10 carbon atoms and A and B independently = bivalent organic groups. The invention further relates to novel polymeric mixtures based on the above and the use of the novel polyurethanes, polymeric mixtures and dispersions thereof for the production of coating materials, adhesives and sealing masses.

Description

The present invention relates to new sulfide-containing polyurethanes and new polymer mixtures on this basis. The present invention also relates to Production of the new, sulfide-containing polyurethanes and Polymer mixtures on this basis. Furthermore, the present invention relates to new ones Dispersions containing the new sulfide-containing polyurethanes and / or the new ones Contain polymer mixtures on this basis. In addition, the present concerns Invention the use of the new, sulfide-containing polyurethanes, the Polymer mixtures on this basis and their dispersions for the production of new ones Coating materials, adhesives and sealants. Furthermore, the present concerns Invention the production of new coatings, adhesives and seals on and in primed and unprimed substrates. Last but not least, this concerns Invention of primed and unprimed substrates with a new coating coated, a new adhesive layer glued and / or with a new seal are sealed.

In the context of the present invention, the polymeric polymer mixtures Materials understood in the polymerization of olefinically unsaturated Monomers in the presence of polyurethanes result. It can be Graft copolymers act with no or only very small amounts Contain polyurethanes and (co) polymers of the olefinically unsaturated monomers. The polymer mixtures can, however, also be made from the polyurethanes and the (Co) polymers exist. Furthermore, it can be mixtures Graft copolymers, polyurethanes and (co) polymers of olefinic act unsaturated monomers.

Polymer mixtures based on polyurethane are known. They are usually prepared by polymerizing olefinically unsaturated monomers in the aqueous dispersion of a hydrophilic or hydrophobic polyurethane which contains terminal and / or lateral olefinically unsaturated groups in the polymer chain. Groups of this type can

• Via maleic acid or fumaric acid and / or their esters into the polyurethane chain,
• - About compounds with two isocyanate-reactive groups and at least one olefinically unsaturated group or via compounds with two Isocanate groups and at least one olefinically unsaturated group laterally Polyurethane chain,
• - About compounds with an isocyanate-reactive group and at least one olefinically unsaturated group or via compounds with an isocanate group and at least one olefinically unsaturated group terminal to Polyurethane chain or
• - About anhydrides alpha, beta-unsaturated carboxylic acids

to be built in. An example of this is the patent applications and patent specifications DE 197 22 862 C2, DE 196 45 761 A1, EP 0 401 565 A1, EP 0 522 420 A1, EP 0 522 419 A2, EP 0 755 946 A1, EP 0 608 021 A1, EP 0 708 788 A1 or EP 0 730 613 A1 as well as the unpublished German patent applications DE 199 53 446.2, DE 199 53 445.2 or DE 199 53 203.6.

In the context of the present invention, the property is hydrophilic to understand the constitutional property of a molecule or a functional group, penetrate or remain in the aqueous phase. Accordingly, under the present invention under the property hydrophobic the constitutional property of a molecule or functional group to understand yourself towards water behave exophilically, d. that is, they show a tendency not to penetrate water or that leave aqueous phase. In addition, varnishes and printing inks are used on Römpp Lexikon, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hydrophilicity", "Hydrophobia", pages 294 and 295.

The known polymer mixtures based on polyurethane are used primarily for Manufacture of waterborne basecoats used. The well-known water-based paints are used in primarily the production of color and / or effect basecoats in  Multicoat paint systems using the wet-on-wet process, as used, for example, in the patents and patent applications listed above.

However, the known polymer mixtures based on polyurethane can be prepared Cause problems.

Lateral and / or terminal allyl groups are often incorporated as grafting centers. However, the reactivity of the allyl groups is comparatively low. You use instead whose the more reactive acrylate or methacrylate groups, it can be used to gel the Polyurethanes come before or during the graft copolymerization.

Last but not least, in some cases the polyurethane content of olefinic unsaturated groups turn out to be too low for complete grafting, so that a large part of the monomers to be grafted on separate homo- and / or copolymers in addition to the polyurethane, which forms the application properties of Polymer mixtures and the coating materials, adhesives and Can impair sealants. This disadvantage is not easily overcome an increase in the double bond content in the polyurethanes to be grafted fix, because this means other important application properties of the Polyurethanes are affected.

Polyurethanes that contain thiol groups, especially terminal thiol groups known.

From the German patent application DE 40 17 940 A1 are alpha, omega-difunctional Prepolymers known to have terminal thiol groups and in the chain Contain thiocarbamate groups. They are made using dithiols Diisocyanates produced. You can manufacture linear polymers, networks, Casting resins, composites, laminates, adhesives, coatings, lacquers and as Starting products for the production of thermoplastic high molecular materials. However, details regarding these uses are not given.

German patent application DE 35 08 428 A1 describes oligourethanes with terminal ones Thiol groups known. They are made by the reaction of polyisocyanates  with a deficit of polyols and mercaptoalkanols. They are used as binders for oxidatively curable coating materials and sealants, as additives for Epoxy resins or as crosslinking agents for olefinically unsaturated compounds containing plastics or plastic precursors used.

German patent application DE 21 21 478 A1 describes a method for networking of polymers containing thiol groups known. As a crosslinking agent Nitrile-N-oxides or their precursors such as poly (hydroxamoyl halides) are used.

From the German patent application DE 34 07 031 A1 is a manufacturing process of chemically curable or water-vulcanizable adhesives, Coating materials, sealing compounds and casting compounds based on polyurethanes known. In this process, prepolymers containing free isocyanate groups are used implemented with prepolymers containing thiol groups by the implementation of prepolymers containing free isocyanate groups are available with mercaptoalkanols.

German patent application DE 20 28 892 A1 describes a curable composition known to have one component with several olefinically or acetylenically unsaturated Contains bonds and a polythiol as a crosslinking agent. The reaction between them Components can be accelerated by alpha-hydroxycarboxylic acids.

The object of the present invention is to provide new polymer mixtures based on polyurethane to provide, which no longer have the disadvantages of the prior art, but which can be easily targeted in the presence of easily accessible hydrophilic and hydrophobic polyurethanes can be produced in high yields and independently whether they contain small or large amounts of homo- and / or copolymers, have very good application properties. The new polymer blends on the basis of polyurethane are said to be suitable for the production of aqueous coating materials, Adhesives and sealants are suitable, which on and / or in primed and Unprimed substrates provide coatings, adhesive layers and seals that at least the property profile of the previously known coatings, adhesive layers and Have seals, if not surpass them.  

Accordingly, we have found the new polyurethane containing sulfide groups which contains at least one group of the general formula I incorporated in the main polymer chain and / or at least one group of the general formula II at the chain end:

-XASBY- (I)

-XASB-YH (II),

where the variables have the following meaning:
S sulfur atom;
X and Y independently of one another oxygen atoms, sulfur atoms or groups - NZ with Z = hydrogen atom or alkyl radical with 1 to 10 carbon atoms; and
A and B are independently divalent organic radicals.

In the following, the new polyurethane containing sulfide groups is called "Polyurethane according to the invention" referred to.

In addition, the new polymer mixture based on the inventive Found polyurethane that can be produced by using at least one olefinic unsaturated monomer in a solution or in an aqueous dispersion at least polymerized a hydrophobic or hydrophilic polyurethane according to the invention.

In the following, the new polymer mixture is called "polymer mixture according to the invention" designated.

Furthermore, the new process for the production of the polyurethane according to the invention was found, in which at least one compound of the general formula III is or are incorporated into the main polymer chain and / or at the chain end:

HX-ASB-YH (III)

where the variables have the following meaning:
S sulfur atom;
H hydrogen atoms;
X and Y independently of one another oxygen atoms, sulfur atoms or groups - NZ with Z = hydrogen atom or alkyl radical with 1 to 10 carbon atoms; and
A and B are independently divalent organic radicals.

Furthermore, the new process for the preparation of a polymer mixture was carried out Polymerization of at least one olefinically unsaturated monomer in the presence at least one hydrophilic or hydrophobic polyurethane according to the invention found.

In addition, the new aqueous dispersions of the polyurethane according to the invention and the polymer mixture according to the invention found.

Furthermore, the new coating materials, adhesives and sealants were on Basis of the polyurethane according to the invention, the polymer mixture according to the invention and / or their dispersions.

Furthermore, the new coatings, adhesive layers and seals on and / or in primed and unprimed substrates found below as "Coatings, adhesive layers and seals according to the invention" are referred to.

Further objects according to the invention result from the description.

In view of the prior art, it was surprising that the complex task that is the basis of the present invention with the help of the invention Polyurethanes and the polymer mixtures according to the invention solved in an elegant manner  could be. It was even more surprising that neither the process for producing the Polyurethanes according to the invention still for the process for producing the Polymer mixtures according to the invention special new apparatus or procedural measures are necessary, but that the state of the art Technically known process measures and devices are used can. It should be emphasized here that in said method according to the invention the procedural and safety problems that arise with the Use of olefinically unsaturated polyurethanes, such as gelling of the approach. The extraordinarily broad applicability of the polyurethanes and polymer mixtures according to the invention and the invention Dispersions.

The preparation of the polymer mixture according to the invention is based on at least one, preferably a, hydrophilic or hydrophobic polyurethane according to the invention.

The polyurethane according to the invention contains at least one group of the general formula I incorporated in the polymer main chain and / or at least one group of the general formula II at the chain end:

-XASBY- (I)

-XASB-YH (II),

where the variables have the following meaning:
S sulfur atom;
X and Y independently of one another oxygen atoms, sulfur atoms or groups - NZ with Z = hydrogen atom or alkyl radical with 1 to 10 carbon atoms; and
A and B are independently divalent organic radicals.

Examples of suitable alkyl radicals Z are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, Octyl, nonyl or decyl.

The divalent organic radicals A and B can be the same or different from one another his. Suitable are all divalent organic radicals A and B that are not are isocyanate-reactive.

Examples of suitable divalent organic radicals are substituted or unsubstituted aliphatic, cycloaliphatic, aromatic, aliphatic-cycloaliphatic, aliphatic aroamtic and / or cycloaliphatic-aromatic divalent radicals, the heteroatoms May contain, but must not be isocyanate-reactive.

Suitable substituents are electron-withdrawing or electron-donating atoms or organic residues that are not isocyanate-reactive.

Examples of suitable substitutes are halogen atoms, in particular chlorine and fluorine, Nitrile groups, nitro groups, partially or fully halogenated, especially chlorinated and / or fluorinated, alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, Alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalky radicals; Aryloxy, alkyloxy and Cycloalkyloxy radicals, in particular phenoxy, naphthoxy, methoxy, ethoxy, propxy, Butyloxy or cyclohexyloxy.

According to the invention, the unsubstituted divalent organic radicals A and B are contain no heteroatoms, advantageous and are therefore preferred according to the invention used.

Particularly suitable divalent aliphatic radicals A and B are derived from aliphatic hydrocarbons such as methane, ethane, propane, butane, pentane, hexane, Heptane, octane, nonane or decane.

Particularly suitable divalent cycloaliphatic radicals A and B are derived from cycloaliphatic hydrocarbons such as cyclobutane, cyclopentane, cyclohexane, Norbornene or decalin.  

Particularly suitable divalent aromatic radicals A and B are derived from aromatic hydrocarbons such as benzene, naphthalene or biphenyl.

Aliphatic-cycloaliphatic divalent radicals A and B are particularly suitable differ from aliphatic-cycloaliphatic hydrocarbons such as ethylcyclopentane or Methylcyclohexane.

Particularly suitable aliphatic-aromatic divalent radicals A and B are derived of aliphatic-aromatic hydrocarbons such as toluene or xylene.

Cycloaliphatic-aromatic divalent radicals A and B are particularly suitable differs from cycloaliphatic-aromatic hydrocarbons such as cyclohexylbenzene or cyclohexylbiphenyl.

The divalent aliphatic radicals A and B are very particularly suitable, especially the ethane-1,2-diyl residue (dimethylene residue).

Accordingly, it is the very particularly preferred group of general formula I around the 1,7-dioxa-4-thia-heptane-1,7-diyl group and in the whole group of the general formula II used with particular preference around the 1,7-dioxa-4- thia-heptan-1-yl group.

The polyurethanes according to the invention preferably contain at least one, in particular at least two chain groups of the general formula I. In addition they can also have at least one, especially at least two, terminal Contain groups of the general formula II. The content of groups of general Formula I or to groups of the general formula I and II can on the stoichiometric ratios of the starting compounds described below for the polyurethanes of the invention are adjusted.

The polyurethanes according to the invention are linear, star-shaped or branched comb-shaped, but especially linear. Except for those essential to the invention Groups of the general formula I and / or the general formula II, they can further contain functional groups.  

So both the hydrophilic and the hydrophobic according to the invention Polyurethanes contain reactive functional groups through which the resulting Polymer mixtures according to the invention thermally self-crosslinking or externally crosslinking become. The prerequisite is, however, that these reactive functional groups are not the Interfering or inhibiting graft copolymerization.

The hydrophilic polyurethanes generally contain either

• 1. functional groups by neutralizing agents and / or Quaternizing agents can be converted into cations, or
• 2. functional groups which are converted into anions by neutralizing agents can, and / or anionic groups and / or
• 3. nonionic hydrophilic groups, in particular poly (alkylene ether) groups,

the the dispersibility of the polyurethanes and the polymer mixtures according to the invention promote in water.

Examples of suitable functional groups (f1) to be used according to the invention which can be converted into cations by neutralizing agents and / or quaternizing agents can, are primary, secondary or tertiary amino groups, secondary sulfide groups or tertiary phosphine groups, especially tertiary amino groups or secondary Sulfide groups.

Examples of suitable cationic groups (f1) to be used according to the invention are primary, secondary, tertiary or quaternary ammonium groups, tertiary Sulfonium groups or quaternary phosphonium groups, preferably quaternary Ammonium groups or tertiary sulfonium groups, but especially tertiary Sulfonium.  

Examples of suitable functional groups (f2) to be used according to the invention which can be converted into anions by neutralizing agents are carboxylic acid, Sulphonic acid or phosphonic acid groups, especially carboxylic acid groups.

Examples of suitable anionic groups (f2) to be used according to the invention are Carboxylate, sulfonate or phosphonate groups, especially carboxylate groups.

Examples of suitable neutralizing agents for functional convertible into cations Groups (f1) are inorganic and organic acids such as sulfuric acid, hydrochloric acid, Phosphoric acid, formic acid, acetic acid, lactic acid, dimethylolpropionic acid or Citric acid.

Examples of suitable neutralizing agents for functional anions convertible into anions Groups (f2) are ammonia or amines, such as. B. trimethylamine, triethylamine, Tributylamine, dimethylaniline, diethylaniline, triphenylamine, dimethylethanolamine, Diethylethanolamine, methyldiethanolamine, 2-aminomethylpropanol, Dimethylisopropylamine, dimethylisopropanolamine or triethanolamine. Is preferred Dimethylethanolamine and / or triethylamine are used as neutralizing agents.

The polyurethane according to the invention advantageously has, depending on the type of stabilization an acid number or amine number of 10 to 250 mg KOH / g (ionic stabilization or nonionic plus ionic stabilization) or from 0 to 10 mg KOH / g (nonionic Stabilization), an OH number of 30 to 350 mg KOH / g and a number-average Molecular weight from 1,500 to 55,000 daltons.

The polyurethanes according to the invention can be produced by any customary and known methods of polyurethane chemistry. According to the invention, however, it is advantageous to react them by reacting a polyurethane prepolymer containing isocyanate groups with at least one compound of the general formula III

HX-ASB-YH (III)

manufacture. In the general formula III, the variables have the above in the general formulas I and II meaning given. Examples of more suitable ones  Compounds of the general formula III are accordingly thiodiethanol, thiodicyclohexane 4-ol or thiodiphenol, but especially thiodiethanol.

The polyurethane prepolymers containing isocyanate groups are linear, star-shaped branched or comb-shaped polymers or oligomers. Preferably linear polyurethane prepolymers are used.

In the context of the present invention, here and below, among oligomers Resins understood that contain at least 2 to 15 monomer units in their molecule. In the context of the present invention, polymers are understood to be resins which contain at least 10 monomer units in their molecule. Complementary to these Terms in Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Oligomers", page 425.

The reaction of the isocyanate-containing polyurethane prepolymers with the Compounds of the general formula III have no special methodological features, but takes place according to the usual and known methods of organic chemistry Polysiocyanates, such as those found in German patent applications DE 34 07 031 A1 or DE 40 17 940 A1 can be described. The implementation is usually like this long until no free isocyanate groups can be detected.

From a methodological point of view, the preparation of those containing isocyanate groups Polyurethane prepolymers have no peculiarities, but take place, for example, as in the patent specifications EP 0 089 497 B1 or EP 0 228 003 B1 Reaction of at least one polyisocyanate, in particular a diisocyanate, with at least one polyol, in particular a diol, the isocyanate component in molar excess is applied so that terminal free isocyanate groups result.

Preference is given to the preparation of those containing isocyanate groups Polyurethane prepolymer diisocyanates and optionally in minor amounts Polyisocyanates used to introduce branches. As part of the In the present invention, subordinate amounts are to be understood as amounts that do not  Effect gelation of the polyurethane prepolymers in their manufacture. The latter can also can also be prevented by using small amounts of monoisocyanates.

Examples of suitable diisocyanates are isophorone diisocyanate (= 5-isocyanato-1- isocyanatomethyl-1,3,3-trimethyl-cyclohexane), 5-isocyanato-1- (2-isocyanatoeth-1-yl) - 1,3,3-trimethyl-cyclohexane, 5-isocyanato-1- (3-isocyanatoprop-1-yl) -1,3,3-trimethyl- cyclohexane, 5-isocyanato- (4-isocyanatobut-1-yl) -1,3,3-trimethyl-cyclohexane, 1- Isocyanato-2- (3-isocyanatoprop-1-yl) cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-1- yl) cyclohexane, 1-isocyanato-2- (4-isocyanatobut-1-yl) cyclohexane, 1,2- Diisocyanatocyclobutane, 1,3-diisocyanatocyclobutane, 1,2-diisocyanatocyclopentane, 1,3- Diisocyanatocyclopentane, 1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4- Diisocyanatocyclohexane, dicyclohexylmethane-2,4'-diisocyanate, trimethylene diisocyanate, Tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, Ethylethylene diisocyanate, trimethylhexane diisocyanate, heptane methylene diisocyanate or Diisocyanates derived from dimer fatty acids, such as those under the trade name DDI 1410 distributed by the Henkel company and in the patents DO 97/49745 and WO 97/49747 be described, in particular 2-heptyl-3,4-bis (9-isocyanatononyl) -1- pentyl-cyclohexane, or 1,2-, 1,4- or 1,3-bis (isocyanatomethyl) cyclohexane, 1,2-, 1,4- or 1,3-bis (2-isocyanatoeth-1-yl) cyclohexane, 1,3-bis (3-isocyanatoprop-1-yl) cyclohexane, 1,2-, 1,4- or 1,3-bis (4-isocyanatobut-1-yl) cyclohexane, liquid bis (4- isocyanatocyclohexyl) methane with a trans / trans content of up to 30% by weight, preferably 25% by weight and in particular 20% by weight, as described in the patents DE 44 14 032 A1, GB 1 220 717 A1, DE-A-16 18 795 or DE 17 93 785 A1; Toluene diisocyanate, xylylene diisocyanate, bisphenylene diisocyanate, naphthylene diisocyanate or diphenylmethane diisocyanate.

Examples of suitable polyisocyanates are the isocyanurates of those described above Diisocyanates.

Examples of highly suitable monoisocyanates are phenyl isocyanate, cyclohexyl isocyanate, Stearyl isocyanate, vinyl isocyanate, methacryloyl isocyanate and / or 1- (1-isocyanato-1- methylethyl) -3- (1-methylethenyl) benzene (TMI® from CYTEC).  

Examples of suitable polyols are saturated or olefinically unsaturated polyester polyols which are obtained by reacting

• - optionally sulfonated saturated and / or unsaturated polycarboxylic acids or their esterifiable derivatives, optionally together with Monocarboxylic acids, as well
• - Saturated and / or unsaturated polyols, optionally together with monools

getting produced.

Examples of suitable polycarboxylic acids are aromatic, aliphatic and cycloaliphatic polycarboxylic acids. Aromatic and / or aliphatic are preferred Polycarboxylic acids used.

Examples of suitable aromatic polycarboxylic acids are phthalic acid, isophthalic acid, Terephthalic acid, phthalic acid, isophthalic acid or terephthalic acid monosulfonate, or Halophthalic acids, such as tetrachloro- or tetrabromophthalic acid, of which Isophthalic acid is advantageous and is therefore preferably used.

Examples of suitable acyclic aliphatic or unsaturated polycarboxylic acids are Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid or Dodecanedicarboxylic acid or maleic acid, fumaric acid or itaconic acid, of which Adipic acid, glutaric acid, azelaic acid, sebacic acid, dimer fatty acids and maleic acid are advantageous and are therefore preferably used.

Examples of suitable cycloaliphatic and cyclic unsaturated polycarboxylic acids are 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2- Cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, hexahydrophthalic acid, 1,3- Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, Tricyclodecanedicarboxylic acid, tetrahydrophthalic acid or 4-methyltetrahydrophthalic acid.  

These dicarboxylic acids can be used both in their cis and in their trans form and as Mixture of both forms can be used.

Further examples of suitable polycarboxylic acids are polymeric fatty acids, in particular those with a dimer content of more than 90% by weight, which are also known as dimer fatty acids be designated.

The esterifiable derivatives of the above are also suitable Polycarboxylic acids, such as. B. their mono- or polyvalent esters with aliphatic alcohols with 1 to 4 carbon atoms. In addition, the anhydrides of the above Polycarboxylic acids are used if they exist.

If necessary, monocarboxylic acids can also be used together with the polycarboxylic acids are used, such as benzoic acid, tert-butylbenzoic acid, lauric acid, Isononanoic acid or fatty acids from naturally occurring oils and acrylic acid, Methacrylic acid, ethacrylic acid or crotonic acid. Monocarboxylic acid is preferred Isononanoic acid used.

Examples of suitable polyols are diols and triols, especially diols. Usually triols are used in minor amounts in addition to the diols Introduce branches into the polyester polyols. As part of the present Invention are to be understood by minor amounts, amounts that do not gel the Cause polyester polyols in their manufacture.

Examples of suitable diols are ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, 1,2-, 1,3-, 1,4- or 1,5-pentanediol, 1,2-, 1,3-, 1,4-, 1,5- or 1,6 hexanediol, Hydroxypivalic acid neopentyl ester, neopentyl glycol, diethylene glycol, 1,2-, 1,3- or 1,4- Cyclohexanediol, 1,2-, 1,3- or 1,4-cyclohexanedimethanol, trimethylpentanediol, Ethylbutylpropanediol, the positionally isomeric diethyloctanediols, 2-butyl-2-ethylpropanediol-1,3, 2-butyl-2-methylpropanediol-1,3, 2-phenyl-2-methylpropanediol-1,3, 2-propyl-2-ethylpropanediol-1,3, 2-Di-tert-butylpropanediol-1,3,2-butyl-2-propylpropanediol-1,3,1-dihydroxymethyl-bi cyclo [2.2.1] heptane, 2,2-diethylpropanediol-1,3,2,2-dipropylpropanediol-1,3,2-cyclo hexyl-2-methylpropanediol-1,3, 2,5-dimethyl-hexanediol-2,5, 2,5-diethylhexanediol-2,5,  2-ethyl-5-methylhexanediol-2,5, 2,4-dimethylpentanediol-2,4, 2,3-dimethylbutanediol-2,3, 1,4- (2'-hydroxypropyl) benzene or 1,3- (2'-hydroxypropyl) benzene.

Of these diols, 1,6-hexanediol and neopentyl glycol are particularly advantageous and are therefore used with particular preference.

The diols mentioned above can also be used directly as diols for the preparation of the Polyurethane prepolymers are used.

Examples of suitable triols are trimethylolethane, trimethylolpropane or glycerol, especially trimethylolpropane.

The aforementioned triplets can also be used as triplets directly for the preparation of the Polyurethane prepolymers are used (see. Patent EP 0 339 433 A1).

If necessary, minor amounts of monools can also be used. Examples of suitable monools are alcohols or phenols such as ethanol, propanol, n- Butanol, sec-butanol, tert-butanol, amyl alcohols, hexanols, fatty alcohols, phenol or Allyl alcohol.

The polyester polyols can be prepared in the presence of small amounts suitable solvent as an entrainer. As an entrainer z. B. aromatic hydrocarbons, such as in particular xylene and (cyclo) aliphatic Hydrocarbons, e.g. B. cyclohexane or methylcyclohexane used.

Further examples of suitable polyols are polyester diols which are obtained by reacting a lactone with a diol. They are characterized by the presence of ent hydroxyl groups and recurring polyester components of the formula - (- CO- (CHR) _m -CH ₂ -O -) -. The index m is preferably 4 to 6 and the substituent R = hydrogen, an alkyl, cycloalkyl or alkoxy radical. No substituent contains more than 12 carbon atoms. The total number of carbon atoms in the substituent does not exceed 12 per lactone ring. Examples include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid and / or hydroxystearic acid.

The unsubstituted epsilon-caprolactone is used for the production of the polyester diols where m is 4 and all R substituents are hydrogen. The implementation with lactone is replaced by low molecular weight polyols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol or dimethylolcyclohexane started. However, others can Reaction components, such as ethylenediamine, alkyldialkanolamines or also urea Caprolactone be implemented. Also suitable as higher molecular weight diols Polylactam diols, which are formed by the reaction of, for example, epsilon-caprolactam low molecular weight diols are produced.

Further examples of suitable polyols are polyether polyols, in particular with a number average molecular weight from 400 to 5,000, in particular from 400 to 3,000. Suitable polyether diols are e.g. B. polyether diols of the general formula H - (- O- (CHR ¹ ) _o -) _p OH, where the substituent R ¹ = hydrogen or a lower, optionally substituted alkyl radical, the index o = 2 to 6, preferably 3 to 4 , and the index p = 2 to 100, preferably 5 to 50. Linear or branched polyether diols such as poly (oxyethylene) glycols, poly (oxypropylene) glycols and poly (oxybutylene) glycols are mentioned as particularly suitable examples.

The non-ionic hydrophilic functional groups can by the polyether diols (f3) or a part thereof introduced into the main chain (s) of the polyurethane prepolymers become.

Others can be used to manufacture the polyurethane prepolymers Output compounds are used to improve the property profile of the Polyurethanes according to the invention and the polymer mixtures according to the invention in to vary advantageously.

If the polyurethanes and polymer mixtures according to the invention are to have self-crosslinking properties, at least one compound having at least one blocked isocyanate group and at least two isocyanate-reactive functional groups can be used. Examples of suitable isocyanate-reactive groups are -SH, - NH ₂ , <NH, -OH, -O- (CO) -NH- (CO) -NH ₂ or -O- (CO) -NH ₂ , of which the primary and secondary Amino groups and the hydroxyl group are advantageous and the hydroxyl groups are particularly advantageous. Examples of suitable blocking agents are the blocking agents known from US Pat. No. 4,444,954 A1, of which the oximes and ketoximes xiii), in particular the ketoximes xiii), especially methyl ethyl ketoxime, offer particular advantages and are therefore used with particular preference. However, the blocked isocyanate groups can also result from the reaction of the free isocyanate groups of the polyurethane prepolymer with the blocking agents.

The introduction of olefinically unsaturated groups - if used - can at least a compound with at least one olefinically unsaturated group and at least two isocyanate-reactive functional groups can be used. Examples of more suitable Isocyanate-reactive functional groups are those described above. Examples suitable olefinically unsaturated groups and compounds for their introduction in patent applications and patents DE 197 22 862 C2, DE 196 45 761 A1, EP 0 401 565 A1, EP 0 522 420 A1, EP 0 522 419 A 2, EP 0 755 946 A1, EP 0 608 021 A1, EP 0 708 788 A1 or EP 0 730 613 A1 as well as in those not previously published German patent applications DE 199 53 446.2, DE 199 53 445.2 or DE 199 53 203.6 described. Alternatively, the olefinically unsaturated groups can also via the Compounds described above with at least one olefinically unsaturated Group and an isocyanate group are introduced.

For the production of the hydrophilic polyurethanes according to the invention, the Polyurethane prepolymers containing isocyanate groups and further compounds with at least one hydrophilic functional group and at least one isocyanate-reactive functional group incorporated.

The introduction of hydrophilic functional (potentially) cationic groups (f1) in The polyurethane prepolymers are made by incorporating compounds that are at least one, in particular two, reactive towards isocyanate groups and at least one for Cation-forming group contained in the molecule; the amount to be used can can be calculated from the desired amine number.

Suitable groups reactive toward isocyanate groups are those above described, especially hydroxyl groups and primary and / or secondary Amino groups, of which the hydroxyl groups are preferably used.  

Examples of suitable compounds of this type are 2,2-dimethylolethyl or propylamine, which are blocked with a ketone, the resulting ketoxime group before Formation of the cationic group (f1) is hydrolyzed again, or N, N-dimethyl-, N, N- Diethyl or N-methyl-N-ethyl-2,2-dimethylolethyl or propylamine.

The introduction of hydrophilic functional (potentially) anionic groups (f2) into the Polyurethane prepolymers are made by incorporating compounds that have at least one reactive towards isocyanate groups and at least one capable of forming anions Group contained in the molecule; the amount to be used can be from the target Acid number can be calculated.

Examples of suitable compounds of this type are those which contain two groups which are reactive toward isocyanate groups in the molecule. Suitable groups which are reactive toward isocyanate groups are, in particular, hydroxyl groups and primary and / or secondary amino groups. Accordingly, for example, alkanoic acids with two substituents on the alpha carbon atom can be used. The substituent can be a hydroxyl group, an alkyl group or, preferably, an alkyl group. These alkanoic acids have at least one, generally 1 to 3 carboxyl groups in the molecule. They have 2 to about 25, preferably 3 to 10, carbon atoms. Examples of suitable alkanoic acids are dihydroxypropionic acid, dihydroxysuccinic acid and dihydroxybenzoic acid. A particularly preferred group of alkanoic acids are the alpha, alpha-dimethylolalkanoic acids of the general formula R ² -C (CH ₂ OH) ₂ COOH, where R ^{2 represents} a hydrogen atom or an alkyl group with up to about 20 carbon atoms. Examples of particularly suitable alkanoic acids are 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid and 2,2-dimenthylolpentanoic acid. The preferred dihydroxyalkanoic acid is 2,2-dimethylolpropionic acid. Compounds containing amino groups are, for example, α, δ-diaminovaleic acid, 3,4-diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid and 2,4-diamino diphenyl ether sulfonic acid.

Hydrophilic functional nonionic poly (oxyalkylene) groups (f3) can be introduced into the polyurethane molecules as lateral or terminal groups. In addition to the polyether diols described above, for example alkoxypoly (oxyalkylene) alcohols with the general formula R ³ O - (- CH ₂ -CHR ⁴ -O-) _r H in R ³ for an alkyl radical having 1 to 6 carbon atoms, R ⁴ for a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms and the index r stands for a number between 20 and 75. (cf. patent applications EP 0 354 261 A1 or EP 0 424 705 A2).

The selection of the hydrophilic functional groups (f1) or (f2) is to be made such that no disturbing reactions, such as salt formation or cross-linking with the functional ones Groups which may be present in the other starting compounds and / or Ingredients of the polyurethanes according to the invention or the inventive Polymer mixtures, dispersions, coating materials, sealants or adhesives are available, are possible. The person skilled in the art can therefore make the selection in a simple manner meet based on his expertise.

Of these hydrophilic functional (potentially) ionic groups (f1) and (f2) and the hydrophilic functional nonionic groups (f3) are (potentially) anionic groups (f2) are advantageous and are therefore used with particular preference.

The preparation of the isocyanate group-containing polyurethane prepolymers from the above The starting compounds described also have no methodological Peculiarities, but takes place in bulk or in an inert organic medium, preferably in an inert organic medium, where polar organic solvents, in particular water-miscible solvents such as ketones, esters, ethers, cyclic amides or Sulfoxides, are preferably used. This can be implemented in several stages or in one stage. It is essential that the implementation continues until the Free isocyanate group content is constant.

The polyurethanes according to the invention can be obtained from the solutions or the dispersions which they occur, isolated and for a wide variety of uses, especially in solvent-containing, water- and solvent-free powdery solid or water and solvent free liquid coating materials, adhesives and Sealants are supplied. S0 they are suitable for the production of pigmented or unpigmented, conventional or aqueous paints, powder paints,  Powder slurry varnishes or 100% systems. Above all, they serve to manufacture the polymer mixtures according to the invention.

For this purpose, at least one olefinically unsaturated monomer (a) is used in the Presence of at least one polyurethane according to the invention in organic solution or polymerized in a dispersion.

If the polymerization is carried out in organic solution, this has the advantage that this process step immediately after the preparation of the invention Polyurethane, d. H. without an intermediate dispersing step can be. This facilitates u. U. the isolation of the invention Polymer blends for special purposes. The usual and known methods of solution polymerization are used.

According to the invention it is advantageous to use the monomer (a) or the monomers (a) in the Dispersion of at least one polyurethane according to the invention in an aqueous medium to polymerize, especially when the resulting invention Polymer mixtures for the production of aqueous coating materials, adhesives and Sealants are used.

The aqueous medium essentially contains water. Here, the aqueous medium in minor amounts organic solvents, neutralizing agents, Crosslinking agents and / or additives customary in paint and / or other dissolved solid, liquid or gaseous organic and / or inorganic, low and / or high molecular weight Contain substances. In the context of the present invention is under the term "minor amount" means an amount that reflects the watery character of the aqueous medium does not cancel. The aqueous medium can also be act pure water.

For the purpose of dispersion, the hydrophilic polyurethanes according to the invention, the (potentially) ionic hydrophilic functional groups described above (f1) or (f2) included, with at least one of those described above Neutralizing agent neutralized and then dispersed. With the hydrophilic thio  polyurethanes according to the invention which are only the nonionic hydrophilic functional Contain groups (f3), the use of neutralizing agents is unnecessary.

The hydrophobic polyurethanes of the invention can also in an aqueous Medium be dispersed. This is advantageously done in a strong shear field carried out. From a methodological point of view, this method has no special features, but can, for example, according to the in European patent application EP 0 401 565 A1 described microfluidizer dispersion process.

Examples of monomers (a) used for the preparation of the invention Suitable polymer mixtures are:

Monomers (a1)

Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta ethylenically unsaturated carboxylic acid, which are derived from an alkylene glycol, the is esterified with the acid, or by reacting the acid with an alkylene oxide are available, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, Crotonic acid or ethacrylic acid, in which the hydroxyalkyl group up to 20 Contains carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3- Hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate, ethacrylate or crotonate; 1,4- Bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indendimethanol or Methyl propanediol monoacrylate, monomethacrylate, monoethacrylate or monocrotonate; or reaction products from cyclic esters, such as. B. epsilon-caprolactone and this hydroxyalkyl; or olefinically unsaturated alcohols such as allyl alcohol or poly oils such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or - triallyl. These higher functional monomers (a1) are generally only in minor quantities used. Within the scope of the present invention are here such quantities under minor amounts of higher-functional monomers understand which do not lead to the crosslinking or gelling of the polyacrylate resins because the polymer mixtures according to the invention should be in the form of crosslinked Microgel particles are present.

Monomers (a2)

(Meth) acrylic acid, crotonic acid or ethacrylic acid alkyl or cycloalkyl esters with up to 20 carbon atoms in the alkyl ester, especially methyl, ethyl, propyl, n-butyl, sec.- Butyl, tert-butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate, methacrylate, crotonate or ethacrylate; cycloaliphatic (meth) acrylic acid, crotonic acid or Ethacrylic acid esters, especially cyclohexyl, isobornyl, dicyclopentadienyl, Octahydro-4,7-methano-1H-indene-methanol- or tert-butylcyclohexyl (meth) acrylate, - crotonate or ethacrylate; (Meth) acrylic acid, crotonic acid or Oxaalkyl ethacrylate or oxacycloalkyl ester such as ethyl triglycol (meth) acrylate and Methoxyoligoglycol (meth) acrylate with a molecular weight Mn of preferably 550; or other ethoxylated and / or propoxylated hydroxyl-free (meth) acrylic acid, Crotonic acid or ethacrylic acid derivatives. These can be in minor quantities Highly functional (meth) acrylic acid, crotonic acid or ethacrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, Butylene glycol, pentane-1,5-diol, hexane-1,6-diol, octahydro-4,7-methano-1H-indene dimethanol or cyclohexane 1,2, 1,3 or 1,4 diol di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or pentaerythritol-di-, -tri- or - tetra (meth) acrylate and the analog ethacrylates or crotonates; contain. As part of the present invention are in subordinate amounts higher functional monomers (a2) to understand such amounts that are not used Carry out crosslinking or gelling of the polyacrylate resins, unless the Polymer mixtures according to the invention are said to be in the form of crosslinked microgel particles available.

Monomers (a3)

At least one acid group, preferably one carboxyl group, per molecule ethylenically unsaturated monomers or a mixture of such monomers. As Component (a3) are particularly preferably acrylic acid and / or methacrylic acid used. However, other ethylenically unsaturated carboxylic acids with up to 6 C atoms can be used in the molecule. Examples of such acids are ethacrylic acid, Crotonic acid, maleic acid, fumaric acid and itaconic acid. Can also be ethylenic Unsaturated sulfonic or phosphonic acids or their partial esters as component (a3) be used. The monomers (a3) are furthermore maleic acid mo no (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester and Phthalic acid mono (meth) acryloyloxyethyl ester and vinylbenzoic acid (all isomers),  alpha-methylvinylbenzoic acid (all isomers) or vinylbenzenesulfonic acid (all isomers). into consideration.

Monomers (a4)

Vinyl esters of monocarboxylic acids with 5 to 18 carbon atoms branched in the alpha position in the molecule. The branched monocarboxylic acids can be obtained by Um Settling of formic acid or carbon monoxide and water with olefins in the presence a liquid, strongly acidic catalyst; the olefins can crack products from paraffinic hydrocarbons, such as mineral oil fractions, can and can be both contain branched and straight-chain acyclic and / or cycloaliphatic olefins. at the implementation of such olefins with formic acid or with carbon monoxide and water creates a mixture of carboxylic acids in which the carboxyl groups predominantly a quaternary carbon atom. Other olefinic starting materials are e.g. B. Propylene trimer, propylene tetramer and diisobutylene. The vinyl esters can also on in a manner known per se from the acids, for. B. by using the acid Acetylene can react. Be particularly preferred - because of the good availability - Vinyl esters of saturated aliphatic monocarboxylic acids with 9 to 11 carbon atoms, the are branched on the alpha-C atom.

Monomers (a5)

Reaction product of acrylic acid and / or methacrylic acid with the glycidyl ester monocarboxylic acid branched in the alpha position with 5 to 18 carbon atoms per molecule. The Implementation of acrylic or methacrylic acid with the glycidyl ester of a carboxylic acid A tertiary alpha carbon atom can be before, during or after the Polymerization reaction take place. This is preferred as component (a5) Reaction product of acrylic and / or methacrylic acid with the glycidyl ester Versatic® acid used. This glycidyl ester is available under the name Cardura® E10 in Available commercially. In addition, varnishes and printing inks, Georg, are added to Römpp Lexikon Thieme Verlag, Stuttgart, New York, 1998, pages 605 and 606.

Monomers (a6)

Essentially acid-free ethylenically unsaturated monomers such as

• Olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, Cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene;
• - (Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl, N, N-dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N-dipropyl, N-butyl, N, N-dibutyl, N- Cyclohexyl- and / or N, N-cyclohexyl-methyl- (meth) acrylic acid amide and / or N- Methylol-, N, N-dimethylol-, N-methoxymethyl-, N, N-di (methoxymethyl) -, N- Ethoxymethyl and / or N, N-di (ethoxyethyl) - (meth) acrylic acid amide, the are used in particular when the inventive Polymer mixtures are said to have self-crosslinking properties;
• Monomers containing epoxy groups, such as the glycidyl ester of acrylic acid, Methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and / or itaconic acid;
• - aminoethyl acrylate, aminoethyl methacrylate, allylamine or N - Methyliminoethylacrylat;
• N, N-di (methoxymethyl) aminoethyl acrylate or methacrylate or N, N Di (butoxymethyl) aminopropyl acrylate or methacrylate;
• Acryloyloxy or methacryloyloxyethyl, propyl or butyl carbamate or allophanate; further examples of suitable monomers, which carbamate groups are contained in the patents US 3,479,328 A1, US 3,674,838 A1, US 4,126,747 A1, US 4,279,833 A1 or US 4,340,497 A1;
• - Vinyl aromatic hydrocarbons, such as styrene, alpha-alkyl styrenes, in particular alpha-methylstyrene, arylstyrenes, especially diphenylethylene, and / or vinyltoluene;
• - Nitriles such as acrylonitrile and / or methacrylonitrile;  
• Vinyl compounds such as vinyl chloride, vinyl fluoride, vinylidene dichloride, vinylidene; N-vinylpyrrolidone; Vinyl ethers such as ethyl vinyl ether, n- Propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and / or vinylcyclohexyl ether; Vinyl esters such as vinyl acetate, vinyl propionate, Vinyl butyrate, vinyl pivalate, vinyl ester of Versatic® acids, which under the Brand names VeoVa® are distributed by Deutsche Shell Chemie (In addition, varnish and printing inks are used on Römpp Lexikon, Georg Thieme Verlag, Stuttgart, New York, 1998, page 598 and pages 605 and 606, referenced) and / or the vinyl ester of 2-methyl-2-ethylheptanoic acid; and or
• Polysiloxane macromonomers which have a number average molecular weight Mn of 1,000 to 40,000, preferably from 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 up to 1.5, ethylenically unsaturated double bonds per molecule, as they have in DE 38 07 571 A1 on pages 5 to 7, DE 37 06 095 A1 in the Columns 3 to 7, EP 0 358 153 B1 on pages 3 to 6, in US 4,754,014 A. 1 in columns 5 to 9, in DE 44 21 823 A1 or in that of international Patent application WO 92/22615 on page 12, line 18, to page 18, line 10, are described, or acryloxysilane-containing vinyl monomers by reaction of hydroxy-functional silanes with epichlorohydrin and subsequent reaction of the reaction product with methacrylic acid and / or Hydroxyalkyl esters of (meth) acrylic acid.

From these suitable monomers (a) described by way of example above, the Expert who is particularly suitable for the respective purpose Monomers (a) based on their known physicochemical properties and Easily choose reactivities. For example, it can monomers (a1), (a3) and / or (a6) choose through the reactive functional groups responsible for thermal crosslinking are necessary to be introduced. If necessary, he can do some for this purpose Carry out a few preliminary tests. In particular, he will focus on it ensure that the monomers (a) have no functional groups, in particular (potentially) ionic functional groups, containing the (potential) ionic functional Groups in the hydrophilic polyurethanes of the invention undesirable Interactions and / or chemical reactions enter.  

Should the polymer mixtures according to the invention in the form of crosslinked Microgel particles are present or contain them, higher functional monomers (a), in particular the higher-functional monomers (a1) and / or described above (a2), applied in amounts which lead to a targeted crosslinking of the grafted and / or lead to non-grafted (co) polymers.

According to the invention, particular advantages result if the monomers (a) are selected in this way be that the property profile of the grafted (co) polymers essentially of the (meth) acrylate monomers (a) described above, the other monomers (a) advantageously vary this property profile widely.

According to the invention, very special advantages result when mixtures of the monomers (a1), (a2) and (a6) and optionally (a3) can be used.

From a methodological point of view, the preparation of the polymer mixtures according to the invention has none Special features, but takes place according to the usual and known methods of radical solution polymerization or emulsion polymerization, Mini-emulsion polymerization or micro-emulsion polymerization in the presence at least one polymerization initiator, as described, for example, in the Patent applications and patents DE 197 22 862 C2, DE 196 45 761 A1, EP 0 401 565 A1, EP 0 522 420 A1, EP 0 522 419 A2, EP 0 755 946 A1, EP 0 608 021 A1, EP 0 708 788 A1 or EP 0 730 613 A1 as well as in the not previously published German Patent applications DE 199 53 446.2, DE 199 53 445.2 or DE 199 53 203.6 are described become.

In emulsion polymerization, the monomers (a) can also be used with a part a polyurethane dispersion according to the invention and water brought into a pre-emulsion which is then slowly added to a template, in which the actual Emulsion polymerization is in progress.

Examples of suitable polymerization initiators are free radical initiators such as Dialkyl peroxides such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides, such as Cumene hydroperoxide or tertiary butyl hydroperoxide; Peresters, such as tert-butyl perbenzoate,  tert-butyl perpivalate, tert-butyl per-3,5,5-trimethyl hexanoate or tert-butyl per-2- ethylhexanoate; Potassium, sodium or ammonium peroxodisulfate; Azodinitriles like azobisisobutyronitrile; C-C-cleaving initiators such as benzpinacol silyl ether; or one Combination of a non-oxidizing initiator with hydrogen peroxide. Prefers water-insoluble initiators are used. The initiators are preferred in one Amount of 0.1 to 25 wt .-%, particularly preferably from 0.75 to 10 wt .-%, based on the total weight of the monomers (a) used.

The monomers (a) are then added to the solutions or the aqueous emulsions With the help of the radical initiators mentioned above at temperatures from 0 to 95 ° C, preferably 40 to 95 ° C, and when using redox systems at Polymerized temperatures from 30 to 70 ° C: When working under excess pressure, the Emulsion polymerization can also be carried out at temperatures above 100 ° C. The same applies to solution polymerization when higher-boiling organic solvents and / or overpressure is applied.

It is preferred that the initiator feed takes some time, generally about 1 to 15 Minutes before the feed of the monomers is started. It is also a procedure preferred, in which the addition of initiator at the same time as the addition of Monomers started and about half an hour after the addition of the monomers has been terminated. The initiator is preferably used in a constant amount Unit of time added. When the addition of initiator is complete, the reaction mixture kept at the polymerization temperature until (as a rule 1 to 1.5 hours) all of the monomers used have been substantially completely implemented. "In the essentially completely implemented "is intended to mean that preferably 100% by weight of the used monomers have been implemented, but that it is also possible that a low residual monomer content of at most up to about 0.5% by weight, based on the Weight of the reaction mixture can remain unreacted.

The usual and known stirred vessels come as reactors for the polymerization, Stirred tank cascades, tubular reactors, loop reactors or Taylor reactors, such as them for example in the patent DE 10 71 241 B1, the patent applications EP 0 498 583 A1 or DE 198 28 742 A1 or in the article by K. Kataoka in Chemical  Engineering Science, Volume 50, No. 9, 1995, pages 1409 to 1416, in Consideration.

According to the invention, it is advantageous to use the polyurethanes according to the invention and the Select monomers (a) so that the grafted (co) polymer and / or the grafted hydrophilic polyurethane according to the invention, but especially the grafted hydrophilic polyurethane according to the invention, hydrophilic functional groups, in particular Carboxylic acid groups and / or carboxylate groups (f2).

In the graft copolymers according to the invention, which are in the inventive Polymer mixtures are included or can be included, the ratio from the graft base or core (polyurethane according to the invention) to the graft shell or Shell vary extremely wide, which is a particular advantage of the invention Is polymer mixtures.

In the preferred use according to the invention (potentially) anionic hydrophilic Functional groups (f2), in particular carboxylic acid groups, result in further particular advantages, since in the graft copolymers according to the invention Ratio of shell acid number to core acid number can also be varied widely can.

The polymer mixtures according to the invention can be obtained from the solutions or the Dispersions in which they occur, isolated and the most varied Purposes of use, especially in solvent-containing, water and solvent-free powdery solid or water- and solvent-free liquid coating materials, Adhesives and sealants. They are particularly suitable for Manufacture of pigmented or unpigmented, conventional or aqueous Paints, powder paints, powder slurry paints or 100% systems.

According to the invention, however, it is advantageous to use the dispersions according to the invention which are in procedure according to the invention either as primary dispersions or as Secondary dispersions by dispersing the solutions of the invention Polymer mixtures are obtained in water as such for the production of aqueous coating materials, adhesives and sealants according to the invention  or to be used as aqueous coating materials, adhesives and sealants. In they show excellent use as coating materials Film-forming properties.

The aqueous coating materials, adhesives and Sealing compounds physically, thermally or thermally and with actinic radiation be curable.

In the context of the present invention, the term "physical hardening" means the Hardening a layer of a coating material, an adhesive or a Sealing compound by filming through release of solvent from the coating material, the adhesive or the sealant, the link within the Coating via loop formation of the polymer molecules of the binders (to which Term cf. Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Binders", pages 73 and 74). Or the film adaptation takes place via the coalescence of binder particles (cf. Römpp Lexikon Lacke and Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 and 275). No crosslinking agents are usually necessary for this. Possibly can the physical hardening by atmospheric oxygen, heat or by radiation with actinic radiation are supported.

In the context of the present invention, the term “self-crosslinking” denotes the Property of a binder to undergo crosslinking reactions with itself. The prerequisite for this is that both types of complementary reactive functional groups are included, which are essential for crosslinking are necessary. On the other hand, such coating materials are considered to be cross-linking; Adhesives and sealants referred to, which is a type of complementary reactive functional groups in the binder, and the other type in a hardener or crosslinking agents are present. In addition, Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 to 276, especially page 275, below.

In the context of the present invention, electromagnetic radiation is actinic Radiation, such as near infrared (NIR), visible light, UV radiation or  X-rays, especially UV radiation, and corpuscular radiation such as To understand electron radiation. Become thermal and hardening with actinic Radiation applied together, one speaks of "dual cure" and "dual cure" Coating material "," dual-cure adhesive "or" dual-cure sealant ".

The aqueous adhesives according to the invention can besides those according to the invention Polymer mixtures of other suitable customary and known ingredients in effective Amounts included. Examples of suitable ingredients are those described below Crosslinking agents and additives, insofar as they are considered for the production of adhesives come.

The aqueous sealants according to the invention can also except the Polymer mixtures according to the invention further suitable customary and known Contain ingredients in effective amounts. Examples of suitable ingredients are likewise the crosslinking agents and additives described below, insofar as they are for the production of sealants.

The primary dispersions and secondary dispersions of the invention Polymer mixtures according to the invention are primarily aqueous for the production Coating materials, especially aqueous paints, are suitable. examples for Aqueous paints according to the invention are fillers, solid-color topcoats, water-based paints and Clearcoats. The primary dispersions according to the invention display very particular advantages and secondary dispersions when used to make waterborne basecoats become.

The polymer mixtures according to the invention are in the waterborne basecoats advantageously in an amount of 1.0 to 50, preferably 2.0 to 40, particularly preferably 3.0 to 35, very particularly preferably 4.0 to 30 and in particular 5.0 to 25% by weight, each based on the total weight of the respective waterborne basecoat, contain.

The other essential component of the waterborne basecoat according to the invention is at least one color and / or effect pigment. The pigments can be made from there are inorganic or organic compounds.  

Examples of suitable effect pigments are metal flake pigments such as commercially available Aluminum bronzes, aluminum bronzes chromated according to DE 36 36 183 A1, and commercially available stainless steel bronzes and non-metallic effect pigments, such as Pearlescent or interference pigments, platelet-shaped effect pigments based on Iron oxide, which has a color from pink to brown-red or liquid crystalline Effect pigments. In addition, varnishes and printing inks, Georg, are added to Römpp Lexikon Thieme Verlag, 1998, pages 176, "effect pigments" and pages 380 and 381 "metal oxide Mica pigments "to" metal pigments ", and the patent applications and patents DE 36 36 156 A1, DE 37 18 446 A1, DE 37 19 804 A1, DE 39 30 601 A1, EP 0 068 311 A 1, EP 0 264 843 A1, EP 0 265 820 A1, EP 0 283 852 A1, EP 0 293 746 A1, EP 0 417 567 A1, US 4,828,826 A or US 5,244,649 A.

Examples of suitable inorganic color pigments are white pigments such as Titanium dioxide, zinc white, zinc sulfide or lithopone; Black pigments such as carbon black, iron Manganese black or spinel black; Colored pigments such as chromium oxide, Chromium oxide hydrate green, cobalt green or ultramarine green, cobalt blue, ultramarine blue or Manganese blue, ultramarine violet or cobalt and manganese violet, iron oxide red, Cadmium sulfoselenide, molybdate red or ultramarine red; Iron oxide brown, mixed brown, Spinel and corundum phases or chrome orange; or iron oxide yellow, nickel titanium yellow, Chromium titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.

Examples of suitable organic color pigments are monoazo pigments, Bisazo pigments, anthraquinone pigments, benzimidazole pigments, quinacridone pigments, Quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, Indanthrone pigments, isoindoline pigments, isoindolinone pigments, azomethine pigments, Thioindigo pigments, metal complex pigments, perinone pigments, perylene pigments, Phthalocyanine pigments or aniline black.

In addition, Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, Pages 180 and 181, "Iron Blue Pigments" to "Iron Oxide Black", Pages 451 to 453 "Pigments" to "Pigment Volume Concentration", page 563 "Thioindigo Pigments", page 567 "Titanium dioxide pigments", pages 400 and 467, "Naturally occurring pigments",  Page 459 "Polycyclic Pigments", page 52, "Azomethine Pigments", "Azo Pigments", and page 379, "Metal Complex Pigments".

The waterborne basecoat can contain at least one crosslinking agent which is suitable for the thermal crosslinking necessary complementary reactive functional groups having.

Examples of suitable crosslinking agents are aminoplast resins, as described, for example, in Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 29, "Aminoharze", the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 ff1, the book "Paints, Coatings and Solvents", second completely revised edition, edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff., The patents US 4,710,542 A or EP 0 245 700 A1 as well as in the article by B. Singh and co-workers "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry ", in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207. Compounds or resins containing carboxyl groups, as described, for example, in US Pat Patent specification DE 196 52 813 A1 are described, containing epoxy groups Compounds or resins as described, for example, in the patents EP 0 299 420 A1, DE 22 14 650 B1, DE 27 49 576 B1, US 4,091,048 A or US 3,781,379 A blocked polyisocyanates, as described, for example, in the patents US 4,444,954 A1, DE 196 17 086 A1, DE 196 31 269 A1, EP 0 004 571 A1 or EP 0 582 051 A1 are described, and / or tris (alkoxycarbonylamino) triazines, as described in the Patents US 4,939,213 A, US 5,084,541 A, US 5,288,865 A or EP 0 604 922 A. to be discribed.

The use of crosslinking agents can be omitted if the in the Water-based paints contain self-crosslinking polymer mixtures according to the invention Have properties or connect physically.

In addition to the components described above, the inventive one Waterborne basecoat common and known binders and / or additives in effective Amounts included.  

Examples of conventional and known binders are oligomeric and polymeric, thermal curable, linear and / or branched and / or block-like, comb-like and / or statistical constructed poly (meth) acrylates or acrylate copolymers, in particular those in the Patent specification DE 197 36 535 A1 described polyester, in particular those in the Patents DE 40 09 858 A1 or DE 44 37 535 A1 described alkyds, acrylated polyesters, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, (Meth) acrylate diols, partially saponified polyvinyl esters, polyurethanes and acrylated Polyurethanes, such as those in patent applications EP 0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A1, EP 0 730 613 A1 or DE 44 37 535 A1, or Polyureas or binders curable with actinic radiation, such as, for example be described in German patent application DE 198 35 206 A1.

Examples of suitable additives are organic and inorganic fillers, thermal curable reactive diluents or reactive diluents curable with actinic radiation (cf. Römpp Lexikon Lacke und Druckfarben, Stuttgart, New York, 1998, pages 491), low boiling organic solvents and / or high boiling organic solvents ("long Solvents "), UV absorbers, light stabilizers, radical scavengers, thermolabile radicals Initiators, photoinitiators, crosslinking catalysts, deaerators, Slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting agents, Adhesion promoters, leveling agents, film-forming aids, rheology-controlling additives or Flame retardants. Further examples of suitable paint additives are given in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, described.

The production of the waterborne basecoat according to the invention has no special features, but is done in a conventional and known manner by mixing the above described components in suitable mixing units such as stirred kettles, dissolvers, Agitator mills, static mixers, gear rim dispersers or extruders according to the processes suitable for the production of the respective water-based paints.

Of course, the pigments, crosslinking agents and other additives and the methods described above also for the production of the adhesives and sealants of the invention are used.  

The waterborne basecoat is excellent for producing colors and / or effects Multicoat paint systems suitable for the wet-on-wet process, in which one Applied water-based stain layer, dried and covered with a clear lacquer layer after which the water-based lacquer layer is hardened together after the clear lacquer layer. As is known, this process is used in the automotive painting and - refinish applied with advantage.

In addition, however, the coating materials of the invention come because of their particularly advantageous properties also for the coating of buildings in the Indoor and outdoor use, for painting furniture, windows or doors and the industrial painting, including coil coating, container coating and impregnation or coating of electrical components. As part of the industrial Painting they are suitable for painting practically all parts for private or industrial use such as radiators, household appliances, small metal parts such as Screws and nuts, hubcaps, rims, packaging or electrical components such as motor windings or transformer windings.

The adhesives and sealants according to the invention are ideal for Manufacture of adhesive layers and seals, even under climatically extreme and / or rapidly changing climatic conditions in the long term of particularly high Adhesion and sealing ability are.

Accordingly, they point to the technological areas listed above Usually used primed or unprimed substrates with at least a coating according to the invention coated with at least one adhesive layer according to the invention glued and / or with at least one Seal according to the invention are sealed in a particularly advantageous application-technical property profile a particularly long service life on what makes them particularly attractive economically.

Examples Production Example 1 The production of a polyester polyol

In a plant suitable for polyester synthesis, 891.2 parts by weight of Pripol® 1013 (commercial dimer fatty acid), 292.8 parts by weight of 1,6-hexanediol, 360.3 Parts by weight of isophthalic acid and 250.7 parts by weight of neopentyl glycol with xylene as Entrainer reacted until an acid number <5 mg KOH / g was reached. The xylene was then distilled off and the polyester was allowed to react further until a Acid number of 3 to 4 mg KOH / g was reached. The polyester was cooled to 110 ° C and dissolved with methyl ethyl ketone to a solids content of 73 wt .-% (theor.). The number average molecular weight was 2,333 daltons, the mass average 4,912 Dalton.

Preparation example 2 The production of a polyurethane prepolymer containing isocyanate groups

In a plant suitable for the implementation of isocyanates, 1,535.1 Parts by weight of the polyester solution according to Preparation Example 1, 160 parts by weight Dimethylolpropionic acid, 16 parts by weight of neopentyl glycol and 636 parts by weight Tetramethylxylylidene diisocyanate (TMXDI) heated to 90 ° C. The resulting mixture was with 413.9 parts by weight of methyl ethyl ketone to a solids content of 70 wt .-% (theor.) diluted and allowed to react until the isocyanate content remains constant was (2.16 wt .-%, based on the solids of the polyurethane prepolymer).

example 1 The production of a polyurethane according to the invention and an aqueous one Dispersion of this

1498 parts by weight of the solution of the isocyanate-containing polyurethane prepolymer of preparation example 1 were presented at 90 ° C in the system. Have been submitted 32.3 parts by weight of thiodiethanol are metered in with stirring. The resulting mixture was stirred at 90 ° C until no more isocyanate groups were detectable.  

The solution of the polyurethane according to the invention (theoretical solids content: 73.9% by weight) was neutralized at 82 ° C with triethylamine.

The neutralized solution was dispersed in 1686.5 parts by weight of water, so that one Dispersion of a solids content of 27.3 wt .-% resulted.

Example 2 The preparation of the primary dispersion of a polymer mixture according to the invention

In a conventional and known polymerization vessel equipped with a stirrer, The reflux condenser and two feed vessels became 2,674.5 parts by weight of the dispersion presented according to Example 1 and heated to 82 ° C. During this 4 Hours, a monomer mixture of 243 parts by weight via the first feed vessel Hydroxypropyl methacrylate, 70 parts by weight of n-butyl acrylate, 139 parts by weight of styrene, 139 parts by weight of tert-butylcyclohexyl acrylate and 104 parts by weight Methyl methacrylate and for 4.5 hours via the second feed vessel 35 Parts by weight of tert-butyl per-2-ethylhexanoate were metered in and copolymerized at 82 ° C. Monomer and initiator feed were started at the same time. After completing the The initiator feed was postpolymerized for 1 hour. The resulting one Primary dispersion (theoretical solids content: 46.7% by weight) was 652.5 Parts by weight of water diluted. Their solids content (1 hour / 130 ° C) was 34.8% by weight. %, their acid number at 23.1 mg KOH / g and their pH at 7.1. The coagulum content was at 0.06% by weight. The number average molecular weight of the invention Graft copolymer was 8,569 Daltons, the mass average molecular weight was 200,560 daltons

The dispersion was poured onto glass and provided after drying and physical hardening crystal clear coatings. It was also excellent for them Suitable for the production of waterborne basecoats or adhesives and sealants.

Claims (11)

1. Polyurethanes containing sulfide groups and containing at least one group of the general formula I incorporated in the polymer main chain and / or at least one group of the general formula II at the chain end:
-XASBY- (I)
-XASB-YH (II),
where the variables have the following meaning:
S sulfur atom;
X and Y independently of one another oxygen atoms, sulfur atoms or groups -NZ with Z = hydrogen atom or alkyl radical with 1 to 10 carbon atoms; and
the
A and B are independently divalent organic radicals. 2. Polyurethanes according to claim 1, characterized in that the alkyl radicals Z Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and / or decyl be used. 3. Polyurethanes according to claim 1 or 2, characterized in that X or Y for Oxygen atoms are standing. 4. Polyurethanes according to claim 1 or 2, characterized in that X and Y for Oxygen atoms are standing.   5. Polyurethanes according to one of claims 1 to 4, characterized in that it the divalent organic radicals A and B are the same or various, substituted or unsubstituted aliphatic, cycloaliphatic, aromatic, aliphatic-cycloaliphatic, aliphatic-aroamtic and / or cycloaliphatic-aromatic divalent radicals. 6. Polyurethanes according to one of claims 1 to 5, characterized in that they at least one group of the general formula I in the main polymer chain or at least one group of the general formula I in the polymer main chain and at least one group of the general formula II incorporated at the chain end contain. 7. Polyurethanes according to one of claims 1 to 6, characterized in that they can be prepared by using at least one compound of the general formula III:
HX-ASB-YH (III)
where the variables have the following meaning:
S sulfur atom;
H hydrogen atoms;
X and Y independently of one another oxygen atoms, sulfur atoms or groups -NZ with Z = hydrogen atom or alkyl radical with 1 to 10 carbon atoms; and
A and B independently of one another divalent organic radicals;
with at least one polyurethane prepolymer containing isocyanate groups. 8. Polymer mixtures based on polyurethane, can be prepared by in solution or in an aqueous dispersion with at least one olefinically unsaturated monomer at least one polyurethane containing sulfide groups according to one of the Claims 1 to 7 polymerized. 9. Use of the polyurethanes containing sulfide groups according to one of the Claims 1 to 7 and the polymer mixtures based on polyurethane according to claim 8 and their solutions or aqueous dispersions as coating materials, Adhesives or sealants or for the production of coating materials, Adhesives or sealants. 10. Use according to claim 10, characterized in that the Coating materials, adhesives or sealing compounds physically, thermally or are curable thermally and with actinic radiation. 11. Use according to claim 9 or 10, characterized in that the Coating materials, adhesives or sealants in the Motor vehicle initial painting and refinishing, the coating of Buildings indoors and outdoors, for painting furniture, windows or doors and industrial painting, including coil coating, containers Coating and impregnation or coating of electrical components, be used.